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Low-Temperature Sputtered Nickel Oxide Compact Thin Film as Effective Electron Blocking Layer for Mesoscopic NiO/CH3NH3PbI3 Perovskite Heterojunction Solar Cells Kuo-Chin Wang,† Po-Shen Shen,† Ming-Hsien Li,† Shi Chen,† Ming-Wei Lin,‡ Peter Chen,*,†,§,∥ and Tzung-Fang Guo†,§,∥ †
Department of Photonics, §Research Center for Energy Technology and Strategy (RCETS), and ∥Advanced Optoelectronic Technology Center (AOTC), National Cheng Kung University, Tainan, Taiwan 701 ‡ National Synchrotron Radiation Research Center (NSRRC), 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu, Taiwan S Supporting Information *
ABSTRACT: We introduce the use of low temperature sputtered NiOx thin film, which substitutes the PEDOT−PSS and solution-processed NiOx as an effective electron blocking layer for mesoscopic NiO/CH3NH3PbI3 perovskite solar cells. The influences of film thickness and oxygen doping on the photovoltaic performances are scrutinized. The cell efficiency has been improved from 9.51 to 10.7% for devices using NiOx fabricated under pure argon atmosphere. With adequate doping under 10% oxygen flow ratio, we achieved power conversion efficiency of 11.6%. The procedure is large area scalable and has the advantage for cost-effective perovskite-based photovoltaics. KEYWORDS: pervoskite solar cell, sputtering, NiOx thin film, mesoscopic heterojunction, low temperature process
O
challenge as most efficient charge separation junctions with perovskite required organic materials. In our previous report, we have replaced the PEDOT:PSS with solution processed NiOx electrode interlayer for hole extraction.14 Furthermore, we have introduced the mesoscopic NiO layer into this OPVlike structure to host the perovskite material in order to improve light harvesting efficiency (LHE) and morphology control.1 Recently, several groups have successfully reported this p-type sensitized NiO/perovskite heterojunction solar cell.15,16 The elimination of the organic hole transporter (or hole collecting layer) shall improve the device stability and provide versatile choices for materials selection and device design. Other inorganic materials such as CuI and CuSCN have been shown to be a potential candidate for this purpose.17−19 Metal oxide p-type semiconductors are alternative hole transport materials for pereovskite-based solar cells owing to their transparency in the visible region, good chemical stability and various selections in terms of the VB energy level. For the organic bulk heterojunction (BHJ) solar cells, p-type metal oxide semiconductors including NiO,20 V2O5,21 and MoO313,22 have been utilized as hole extraction layer. In dye-sensitized solar cells (DSCs), many metal oxides such as NiO, Cu-based delafossite (CuMO2, M = Al, Ga, or Cr), have been applied as electrode for p-type sensitization.23,24 Recently, NiO/perovskite
rganic−inorganic hybrid metal halide perovskite materials have received intensive attentions since their breakthrough after the successes in solid heterojunction devices in 2012.2,3 The rapid progresses of this research field over the past few years have remarkably advanced the conversion efficiencies over 15%.4−6 Perovskite-based solar cell is considered as a promising emerging technology due to their characteristics of cost-effective solution process, high power conversion efficiency (PCE) and superior photonic properties in terms of light absorption and carrier transport. Various device configurations have been proposed and demonstrated with high PCE. Dye-sensitized solar cells (DSCs) like mesoscopic devices were initially the structure employed which the perovskite material served as a light harvester.2,4,7 Planar heterojunction (PHJ) thin film architectures,5,6,8−10 on the other hand, sandwiched the perovskite between effective charge selective contact materials to accomplish the photovoltaic action. Among the PHJ devices, a typical structure is composed of materials similar to organic photovoltaics like poly(3,4-ethyl- enedioxythiophene) poly(styrene-sulfonate) (PEDOT:PSS) and [6,6]-phenyl C61butyric acid methyl ester (PCBM) where the perovskite material is inserted as absorber and electron donor. This type of OPV-like thin film perovskite solar cells using a lowtemperature process has achieved 11.5%.11 However, the experiences from OPV research have shown concerns of PEDOT:PSS for long-term stability.12,13 Providing more stable constituents for perovskite-based photovoltaics remained a © 2014 American Chemical Society
Received: June 7, 2014 Accepted: July 23, 2014 Published: July 23, 2014 11851
dx.doi.org/10.1021/am503610u | ACS Appl. Mater. Interfaces 2014, 6, 11851−11858
ACS Applied Materials & Interfaces
Letter
heterojunction solar cells have been successfully demonstrated with decent efficiencies.1,15,16 In this article, we developed a low-temperature sputtered NiOx thin film as a functional hole extraction and electron blocking layer for the organic and inorganic hybrid perovskite-based solar cells. The efficiencies are greatly enhanced and the device reproducibility is significantly improved compared with the devices fabricated by solution-processed NiOx thin film. We studied the effects of film thickness and doping ratio of oxygen flow during the lowtemperature sputtered NiOx on the photovoltaic performances of mesoscopic NiO/CH3NH3PbI3 heterojunction solar cells. The characterization of material properties of sputtered NiOx thin film was carried out by X-ray diffraction (XRD) and Mott−Schottky analysis. Optical property of sputtered NiOx compact layer was characterized by UV−visible spectroscopy. Scanning electron microscope (SEM) was conducted to examine the morphology of NiOx thin film. X-ray photoelectron spectroscopy (XPS) was performed to characterize the surface chemical environment. The device architecture is illustrated in Scheme 1. The details of the experimental methods are described in the Supporting
Table 1. Notation List of NiOx Compact Layer Prepared under Various Sputtering Parameters (oxygen flow ratio and sputtering time) oxygen flow ratio (O2/ Ar+O2) (%) notation of filma A-0-0 A-0-100 A-0-125 A-0-150 A-0-175 A-0-200 B-5-150 B-10-150 B-15-150
0
5
10
15
○ ○ ○ ○ ○ ○
sputtering time (s) 0
100
125
150
175
200
⧫ ⧫ ⧫ ⧫ ⧫ ⧫ ○ ○ ○
⧫ ⧫ ⧫
a
A denotes the sample fabricated with pure Ar working gas, whereas B presents the samples deposited with reactive mixture of Ar+O2. The second digit describes the oxygen flow ratio (O2/Ar+O2). The third digit displays the deposition time.
Scheme 1. Device Structure of NiO/Perovskite Heterojunction Solar Cells
Information. The process variables for RF sputtering deposition conditions of NiOx compact layer were summarized in Table 1. The main deposition parameters investigated are oxygen flow ratios and sputtering time. Samples of series A were fabricated by different deposition time under pure Ar as working gas without oxygen doping, and those of series B were prepared under reactive atmosphere with various oxygen flow ratios performed with the same deposition time of 150 s. The devices using the corresponding NiOx sputter film will be denoted as the notations listed in Table 1 through the whole article. The X-ray diffraction patterns for A-0-150, B-5-150, B-10150, and B-15-150 are displayed in Figure 1a. The XRD patterns are assigned to the three main NiO peaks which refer to planes (111), (200), and (220), respectively. The XRD results confirm the existence of NiOx thin film deposited on ITO-coated substrate. On the other hand, it is observed that plane (220) of B-15−150 is slightly broader than that of the others. This is probably due to the interstitial oxygen defects that being introduced by the excess doping from high oxygen/ Ar flow ratio during sputtering deposition.25 Figure 1b−e showed top views of SEM images of NiOx films prepared by various oxygen flow ratios. The grain size of all NiOx films is fairly small (
Low-Temperature Sputtered Nickel Oxide Compact Thin Film as Effective Electron Blocking Layer for Mesoscopic NiO/CH3NH3PbI3 Perovskite Heterojunction Solar Cells Kuo-Chin Wang,† Po-Shen Shen,† Ming-Hsien Li,† Shi Chen,† Ming-Wei Lin,‡ Peter Chen,*,†,§,∥ and Tzung-Fang Guo†,§,∥ †
Department of Photonics, §Research Center for Energy Technology and Strategy (RCETS), and ∥Advanced Optoelectronic Technology Center (AOTC), National Cheng Kung University, Tainan, Taiwan 701 ‡ National Synchrotron Radiation Research Center (NSRRC), 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu, Taiwan S Supporting Information *
ABSTRACT: We introduce the use of low temperature sputtered NiOx thin film, which substitutes the PEDOT−PSS and solution-processed NiOx as an effective electron blocking layer for mesoscopic NiO/CH3NH3PbI3 perovskite solar cells. The influences of film thickness and oxygen doping on the photovoltaic performances are scrutinized. The cell efficiency has been improved from 9.51 to 10.7% for devices using NiOx fabricated under pure argon atmosphere. With adequate doping under 10% oxygen flow ratio, we achieved power conversion efficiency of 11.6%. The procedure is large area scalable and has the advantage for cost-effective perovskite-based photovoltaics. KEYWORDS: pervoskite solar cell, sputtering, NiOx thin film, mesoscopic heterojunction, low temperature process
O
challenge as most efficient charge separation junctions with perovskite required organic materials. In our previous report, we have replaced the PEDOT:PSS with solution processed NiOx electrode interlayer for hole extraction.14 Furthermore, we have introduced the mesoscopic NiO layer into this OPVlike structure to host the perovskite material in order to improve light harvesting efficiency (LHE) and morphology control.1 Recently, several groups have successfully reported this p-type sensitized NiO/perovskite heterojunction solar cell.15,16 The elimination of the organic hole transporter (or hole collecting layer) shall improve the device stability and provide versatile choices for materials selection and device design. Other inorganic materials such as CuI and CuSCN have been shown to be a potential candidate for this purpose.17−19 Metal oxide p-type semiconductors are alternative hole transport materials for pereovskite-based solar cells owing to their transparency in the visible region, good chemical stability and various selections in terms of the VB energy level. For the organic bulk heterojunction (BHJ) solar cells, p-type metal oxide semiconductors including NiO,20 V2O5,21 and MoO313,22 have been utilized as hole extraction layer. In dye-sensitized solar cells (DSCs), many metal oxides such as NiO, Cu-based delafossite (CuMO2, M = Al, Ga, or Cr), have been applied as electrode for p-type sensitization.23,24 Recently, NiO/perovskite
rganic−inorganic hybrid metal halide perovskite materials have received intensive attentions since their breakthrough after the successes in solid heterojunction devices in 2012.2,3 The rapid progresses of this research field over the past few years have remarkably advanced the conversion efficiencies over 15%.4−6 Perovskite-based solar cell is considered as a promising emerging technology due to their characteristics of cost-effective solution process, high power conversion efficiency (PCE) and superior photonic properties in terms of light absorption and carrier transport. Various device configurations have been proposed and demonstrated with high PCE. Dye-sensitized solar cells (DSCs) like mesoscopic devices were initially the structure employed which the perovskite material served as a light harvester.2,4,7 Planar heterojunction (PHJ) thin film architectures,5,6,8−10 on the other hand, sandwiched the perovskite between effective charge selective contact materials to accomplish the photovoltaic action. Among the PHJ devices, a typical structure is composed of materials similar to organic photovoltaics like poly(3,4-ethyl- enedioxythiophene) poly(styrene-sulfonate) (PEDOT:PSS) and [6,6]-phenyl C61butyric acid methyl ester (PCBM) where the perovskite material is inserted as absorber and electron donor. This type of OPV-like thin film perovskite solar cells using a lowtemperature process has achieved 11.5%.11 However, the experiences from OPV research have shown concerns of PEDOT:PSS for long-term stability.12,13 Providing more stable constituents for perovskite-based photovoltaics remained a © 2014 American Chemical Society
Received: June 7, 2014 Accepted: July 23, 2014 Published: July 23, 2014 11851
dx.doi.org/10.1021/am503610u | ACS Appl. Mater. Interfaces 2014, 6, 11851−11858
ACS Applied Materials & Interfaces
Letter
heterojunction solar cells have been successfully demonstrated with decent efficiencies.1,15,16 In this article, we developed a low-temperature sputtered NiOx thin film as a functional hole extraction and electron blocking layer for the organic and inorganic hybrid perovskite-based solar cells. The efficiencies are greatly enhanced and the device reproducibility is significantly improved compared with the devices fabricated by solution-processed NiOx thin film. We studied the effects of film thickness and doping ratio of oxygen flow during the lowtemperature sputtered NiOx on the photovoltaic performances of mesoscopic NiO/CH3NH3PbI3 heterojunction solar cells. The characterization of material properties of sputtered NiOx thin film was carried out by X-ray diffraction (XRD) and Mott−Schottky analysis. Optical property of sputtered NiOx compact layer was characterized by UV−visible spectroscopy. Scanning electron microscope (SEM) was conducted to examine the morphology of NiOx thin film. X-ray photoelectron spectroscopy (XPS) was performed to characterize the surface chemical environment. The device architecture is illustrated in Scheme 1. The details of the experimental methods are described in the Supporting
Table 1. Notation List of NiOx Compact Layer Prepared under Various Sputtering Parameters (oxygen flow ratio and sputtering time) oxygen flow ratio (O2/ Ar+O2) (%) notation of filma A-0-0 A-0-100 A-0-125 A-0-150 A-0-175 A-0-200 B-5-150 B-10-150 B-15-150
0
5
10
15
○ ○ ○ ○ ○ ○
sputtering time (s) 0
100
125
150
175
200
⧫ ⧫ ⧫ ⧫ ⧫ ⧫ ○ ○ ○
⧫ ⧫ ⧫
a
A denotes the sample fabricated with pure Ar working gas, whereas B presents the samples deposited with reactive mixture of Ar+O2. The second digit describes the oxygen flow ratio (O2/Ar+O2). The third digit displays the deposition time.
Scheme 1. Device Structure of NiO/Perovskite Heterojunction Solar Cells
Information. The process variables for RF sputtering deposition conditions of NiOx compact layer were summarized in Table 1. The main deposition parameters investigated are oxygen flow ratios and sputtering time. Samples of series A were fabricated by different deposition time under pure Ar as working gas without oxygen doping, and those of series B were prepared under reactive atmosphere with various oxygen flow ratios performed with the same deposition time of 150 s. The devices using the corresponding NiOx sputter film will be denoted as the notations listed in Table 1 through the whole article. The X-ray diffraction patterns for A-0-150, B-5-150, B-10150, and B-15-150 are displayed in Figure 1a. The XRD patterns are assigned to the three main NiO peaks which refer to planes (111), (200), and (220), respectively. The XRD results confirm the existence of NiOx thin film deposited on ITO-coated substrate. On the other hand, it is observed that plane (220) of B-15−150 is slightly broader than that of the others. This is probably due to the interstitial oxygen defects that being introduced by the excess doping from high oxygen/ Ar flow ratio during sputtering deposition.25 Figure 1b−e showed top views of SEM images of NiOx films prepared by various oxygen flow ratios. The grain size of all NiOx films is fairly small (
